Asymmetric Construction of the Core of C6, C7-Epoxy Daphnane Diterpenoid Orthoesters

Org Lett. 2023 Nov 17;25(45):8072-8076. doi: 10.1021/acs.orglett.3c03136. Epub 2023 Nov 2.

Abstract

Asymmetric construction of the core of C6, C7-epoxy daphnane diterpenoid orthoesters is developed through a convergent synthetic strategy. The salient features include a diastereoselective nucleophilic assembly of two bulky cyclic fragments, an oxidative cleavage/transesterification/aldol cascade to fashion the seven-membered ring, and a base-mediated transesterification/retro-aldol/aldol/epoxidation cascade to install the epoxy moiety with proper stereochemistry.